Abstract
Alternative primary reactions of thermal decomposition of N′-methoxy-N-methyldiazene N-oxide (1) to the experimentally observed products under normal conditions and the average experimental temperature were studied using the density functional methods PBE, B3LYP, wB97XD, wB97X with different basis sets and the composite method G4. All methods gave qualitatively consistent results. Based on these results and a detailed PBE/L11 and B3LYP/6-31G (2df, p) study of various secondary processes, it was concluded that the most energetically advantageous and, hence, the most likely channel of thermal decomposition of 1 involves the isomerization of the latter by rotation of the MeO group around the NO bond followed by the transfer of the Me group between oxygen atoms. The enthalpy of activation of the Me group transfer obtained by all the methods used agrees well with the experimentally obtained value, and this reaction is the limiting step of the entire process of thermal decomposition of 1.
References
E. P. Kirpichev, I. N. Zyuzin, V. V. Avdonin, Yu. I. Rubtsov, D. B. Lempert, Russ. J. Phys. Chem. A., 2006, 80, 1359; DOI: https://doi.org/10.1134/S0036024406090019.
P. G. Wang, M. Xian, X. Tang, X. Wu, Z. Wen, T. Cai, A. J. Janczuk, Chem. Rev., 2002, 102, 1091; DOI: https://doi.org/10.1021/cr000040l.
J. A. Hrabie, L. K. Keefer, Chem. Rev., 2002, 102, 1135; DOI: https://doi.org/10.1021/cr000028t.
T. B. Cai, X. Tang, J. Nagorski, P. G. Brauschweiger, P. G. Wang, Bioorg. Med. Chem., 2003, 11, 4971; DOI: https://doi.org/10.1016/j.bmc.2003.09.003.
J. Brand, T. Huhn, U. Groth, J. C. Jochims, Chem. Eur. J., 2006, 12, 499; DOI: https://doi.org/10.1002/chem.200500325.
I. N. Zyuzin, D. B. Lempert, G. N. Nechiporenko, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1988, 37, 1329; DOI: https://doi.org/10.1007/BF00962732.
G. A. Smirnov, O. A. Lukyanov, Russ. Chem. Bull., 2020, 69, 295; DOI: https://doi.org/10.1007/s11172-020-2759-x.
I. N. Zyuzin, Russ. Chem. Bull., 2020, 69, 1949; DOI: https://doi.org/10.1007/s11172-020-2984-3.
G. A. Smirnov, P. B. Gordeev, Russ. Chem. Bull., 2020, 69, 2153; DOI: https://doi.org/10.1007/s11172-020-3014-1.
D. A. Gulyaev, M. S. Klenov, A. M. Churakov, Yu. A. Strelenko, A. N. Pivkina, V. A. Tartakovsky, Russ. Chem. Bull., 2021, 70, 1599; DOI: https://doi.org/10.1007/s11172-021-3256-6.
A. A. Konnov, I. M. Dubrovin, M. S. Klenov, O. V. Anikin, A. M. Churakov, Yu. A. Strelenko, A. N. Pivkina, V. A. Tartakovsky, Russ. Chem. Bull., 2021, 70, 2189; DOI: https://doi.org/10.1007/s11172-021-3331-z.
V. P. Grachev, I. N. Zyuzin, S. V. Kurmaz, E. V. Vaganov, R. I. Komendant, D. B. Lempert, Russ. Chem. Bull., 2020, 69, 2312; DOI: https://doi.org/10.1007/s11172-020-3037-7.
V. V. Zakharov, N. V. Chukanov, I. N. Zyuzin, V. V. Nedel’ko, B. L. Korsunskii, Russ. J. Phys. Chem. B, 2019, 13, No. 1, 62; DOI: https://doi.org/10.1134/S1990793119010305.
G. B. Manelis, G. M. Nazin, Yu. I. Rubtsov, V. A. Strunin, Termicheskoe razlozhenie i gorenie vzryvchatykh veschestv i porokhov [Thermal Decomposition and Combustion of Explosives and Gunpowders], Izd-vo Nauka, Moscow, 1996, 223 pp. (in Russian).
E. N. Alikina, Analiticheskaya khimiya. Kolichestvennyi analiz: uchebnoe posobie [Analytical Chemistry. Quantitative Analysis: A Study Guide], Izd-vo Perm. Gos. Univ., Perm, 2021, 252 pp. (in Russian).
W. Traube, Ann. Chemie (Paris), 1898, 300, 81.
G. A. Marchenko, L. F. Chertanova, Yu. T. Struchkov, B. I. Buzykin, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1987, 36, 1646; DOI: https://doi.org/10.1007/BF00960123.
O. A. Litvinov, O. N. Kataeva, V. A. Naumov, G. A. Marchenko, V. I. Kovalenko, J. Struct. Chem. (USSR), 1988, 29, No. 3, 469; DOI: https://doi.org/10.1007/BF00744007.
V. V. Zverev, R. G. Islamov, F. Kh. Islamova, V. M. Vakar’, J. Struct. Chem. (USSR), 1989, 30, No. 2, 288; DOI: https://doi.org/10.1007/BF00761310.
V. V. Zverev, F. Kh. Islamova, R. G. Islamov, J. Struct. Chem. (USSR), 1989, 30, No. 2, 233; DOI: https://doi.org/10.1007/BF00761311.
I. N. Zyuzin, G. N. Nechiporenko, Russ. Chem. Bull., 1998, 47, 2317; DOI: https://doi.org/10.1007/BF02494309.
I. N. Zyuzin, D. B. Lempert, G. N. Nechiporenko, Russ. Chem. Bull., 2003, 52, 1431; DOI: https://doi.org/10.1023/a:1024851816572.
I. N. Zyuzin, D. B. Lempert, Russ. J. Gen. Chem., 2010, 80, 1792; DOI: https://doi.org/10.1134/S1070363210090124.
I. N. Zyuzin, D. B. Lempert, Kinet. Catal. (Engl. Transl.), 2011, 52, 17; DOI: https://doi.org/10.1134/S0023158411010228.
T. I. Magsumov, A. G. Shamov, Tez. dokl. XIX Mendeleevskogo s’ezda po obshchei i prikladnoi khimii (Volgograd, 25–30 sentyabrya, 2011 g.) [Abst. XIX Mendeleev Congress on General and Applied Chemistry (Volgograd, Sept. 25–30, 2011)], Volgograd. Gos. Tekhn. Univ., V. 1, p. 278 (in Russian).
I. N. Zyuzin, D. B. Lempert, Russ. J. Gen. Chem., 2012, 82, 1891; DOI: https://doi.org/10.1134/S107036321211031X.
I. N. Zyuzin, D. B. Lempert, Russ. J. Gen. Chem., 2014, 84, 162; DOI: https://doi.org/10.1134/S1070363214010253.
H. Li, F. Zhao, Q. Yu, W. Lai, B. Wang, Chin. J. Energ. Mat., 2014, 22, 880; DOI: https://doi.org/10.11943/j.issn.1006-9941.2014.06.032.
I. N. Zyuzin, D. B. Lempert, Russ. J. Gen. Chem., 2014, 84, 831; DOI: https://doi.org/10.1134/S1070363214050077.
M. S. Klenov, O. V. Anikin, A. M. Churakov, Y. A. Strelenko, I. V. Fedyanin, I. V. Ananyev, V. A. Tartakovsky, Eur. J. Org. Chem., 2015, 6170; DOI: https://doi.org/10.1002/ejoc.201500923.
M. S. Klenov, O. V. Anikin, A. A. Guskov, A. M. Churakov, Y. A. Strelenko, I. V. Ananyev, I. S. Bushmarinov, A. O. Dmitrenko, K. A. Lyssenko, V. A. Tartakovsky, Eur. J. Org. Chem., 2016, 3845; DOI: https://doi.org/10.1002/ejoc.201600584.
Z. G. Aliev, I. N. Zyuzin, S. M. Aldoshin, Russ. J. Struct. Chem., 2016, 57, 760; DOI: https://doi.org/10.1134/S0022476616040193.
N. E. Leonov, M. S. Klenov, O. V. Anikin, A. M. Churakov, Y. A. Strelenko, K. A. Monogarov, K. A. Tartakovsky, Eur. J. Org. Chem., 2019, 91; DOI: https://doi.org/10.1002/ejoc.201801533.
I. N. Zyuzin, A. I. Kazakov, D. B. Lempert, A. V. Nabatova, in Khimiya nitrosoedinenii i rodstvennykh azotkislorodnykh system. Vserosiiskaya konferentsiya, Moskva, 23–25 oktyabrya 2019 [Chemistry of Nitro Compounds and Related Nitrogen-Oxygen Systems: All-Russian Conference, Moscow, Oct. 23–25, 2019], Eds. M. P. Egorov, V. A. Tartakovsky, S. G. Zlotin, Izd-vo MAX Press, Moscow, 2019, p. 156 (in Russian).
I. N. Zyuzin, A. I. Kazakov, D. B. Lempert, I. A. Vatsadze, L. S. Kurochkina, A. V. Nabatova, Comb., Explos., Shock Waves (Engl. Transl.), 2019, 55, 644; DOI: https://doi.org/10.1134/S0010508219060029.
I. N. Zyuzin, D. B. Lempert, A. V. Nabatova, A. I. Kazakov, Comb., Expl., Shock Waves (Engl. Transl.), 2020, 56, 464; DOI: https://doi.org/10.1134/S0010508220040103.
A. G. Shamov, T. I. Magsumov, E. V. Nikolaeva, Tez. dokl. X Mezhdunar. nauch. conf. “Khimicheskaya termodinamika i kinetika” (Velikii Novgorod, 17–21 maya, 2020 g.) [Abst. X Int.. Sci. Conf. “Chemical Thermodynamics and Kinetics” (Velikiy Novgorod, May 17–21, 2020)], The Yaroslav-the-Wise Novgorod State University, 2020, p. 270 (in Russian).
E. V. Nikolaeva, G. M. Khrapkovskii, I. V. Aristov, D. L. Egorov, A. G. Shamov, J. Phys.: Conf. Ser., 2021, 2052, 012030; DOI: https://doi.org/10.1088/1742-6596/2052/1/012030.
E. V. Nikolaeva, A. G. Shamov, G. M. Khrapkovsii, Russ. J. Gen. Chem., 2014, 84, 2076; DOI: https://doi.org/10.1134/S1070363214110048.
E. V. Nikolaeva, D. V. Chachkov, A. G. Shamov, G. M. Khrapkovskii, Russ. Chem. Bull., 2018, 67, 274; DOI: https://doi.org/10.1007/s11172-018-2070-2.
E. V. Nikolaeva, D. L. Egorov, D. V. Chachkov, A. G. Shamov, G. M. Khrapkovskii, Russ. Chem. Bull., 2019, 68, 1510; DOI: https://doi.org/10.1007/s11172-019-2585-1.
D. N. Laikov, Ph. D. (Phys.-Math.), Moscow State Univ., Moscow, 2000, 97 pp. (in Russian).
D. L. Egorov, A. G. Shamov, G. M. Khrapkovsky, Vestn. tekhnol. un-ta [Bull. Technol. Univ.], 2015, 18, No. 21, 12 (in Russian).
A. D. Becke, Phys. Rev. A, 1988, 38, 3098; DOI: https://doi.org/10.1103/PhysRevA.38.3098.
C. Lee, W. Yang, R. G. Parr, Phys. Rev. B, 1988, 37, 785; DOI: https://doi.org/10.1103/PhysRevB.37.785.
G. A. Petersson, A. Bennett, T. G. Tensfeldt, M. A. Al-Laham, W. A. Shirley, J. Mantzaris, J. Chem. Phys., 1988, 89, 2193; DOI: https://doi.org/10.1063/1.455064.
G. A. Petersson, M. A. Al-Laham, J. Chem. Phys., 1991, 94, 6081; DOI: https://doi.org/10.1063/1.460447.
J.-D. Chai, M. Head-Gordon, Phys. Chem. Chem. Phys., 2008, 10, 6615; DOI: https://doi.org/10.1039/b810189b.
F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, 3297; DOI: https://doi.org/10.1039/b508541a.
L. A. Curtiss, P. C. Redfern, K. Raghavachari, J. Chem. Phys., 2007, 126, 084108; DOI: https://doi.org/10.1063/1.2436888.
G. M. Khrapkovskii, A. G. Shamov, R. V. Tsyshevsky, D. V. Chachkov, B. Nguen Van, D. L. Egorov, I. V. Aristov, Comput. Theor. Chem., 2011, 966, 265; DOI: https://doi.org/10.1016/j.comptc.2011.03.016.
G. M. Khrapkovskii, D. D. Sharipov, A. G. Shamov, D. L. Egorov, D. V. Chachkov, B. Nguyen Van, R. V. Tsyshevsky, Comput. Theor. Chem., 2013, 1017, 7; DOI: https://doi.org/10.1016/j.comptc.2013.04.013.
A. F. Shamsutdinov, T. F. Shamsutdinov, D. V. Chachkov, A. G. Shamov, G. M. Khrapkovskii, Int. J. Quant. Chem., 2007, 107, 2343; DOI: https://doi.org/10.1002/qua.21394.
D. D. Sharipov, D. L. Egorov, D. V. Chachkov, A. G. Shamov, G. M. Khrapkovskii, Russ. J. Gen. Chem., 2011, 81, 2273; DOI: https://doi.org/10.1134/S1070363211110107.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, D. J. Fox, Gaussian 16 Revision B.01, Gaussian Inc., Wallingford CT, 2016.
H. B. Schlegel, J. Comp. Chem., 1982, 3, 214; DOI: https://doi.org/10.1002/jcc.540030212.
G. M. Khrapkovskii, A. G. Shamov, E. V. Nikolaeva, D. V. Chachkov, Russ. Chem. Rev., 2009, 78, 903; DOI: https://doi.org/10.1070/RC2009v078n10ABEH004053.
E. V. Nikolaeva, A. G. Shamov, G. M. Khrapkovskii, Kh. E. Kharlampidi, Russ. J. Gen. Chem., 2002, 72, 748; DOI: https://doi.org/10.1023/A:1019564403662.
Y. Peng, X. Xiu, G. Zhu, Y. Yang, J. Phys. Chem. A, 2018, 122, 8336; DOI: https://doi.org/10.1021/acs.jpca.8b06458.
C. Peng, P. Y. Ayala, H. B. Schlegel, M. J. Frisch, J. Comput. Chem., 1996, 17, 49; DOI: https://doi.org/10.1002/(SICI)1096987X(19960115)17:1.
B. L. Korsunskii, G. M. Nazin, V. R. Stepanov, A. A. Fedotov, Kinet. Catal. (Engl. Transl.), 1993, 34, 691.
L. Cooper, L. G. Shpinkova, E. E. Rennie, D. M. P. Holland, D. A. Shaw, Int. J. Mass. Spectrom., 2001, 207, 223; DOI: https://doi.org/10.1016/S1387-3806(01)00374-8.
G. M. Khrapkovskii, E. V. Nikolaeva, D. L. Egorov, D. V. Chachkov, A. G. Shamov, Russ. J. Org. Chem., 2016, 52, 791; DOI: https://doi.org/10.1134/S1070428016060063.
G. M. Khrapkovskii, E. V. Nikolaeva, D. L. Egorov, D. V. Chachkov, A. G. Shamov, Russ. J. Org. Chem., 2017, 53, 999; DOI: https://doi.org/10.1134/S1070428017070077.
A. G. Shamov, E. V. Nikolaeva, G. M. Khrapkovskii, Russ. J. Appl. Chem., 2009, 82, 1741; DOI: https://doi.org/10.1134/S1070427209100024.
K. Fukui, Acc. Chem. Res., 1981, 14, 363; DOI: https://doi.org/10.1021/ar00072a001.
R. Seeger, J. A. Pople, J. Chem. Phys., 1977, 66, 3045; DOI: https://doi.org/10.1063/1.434318.
R. Bauernschmitt, R. Ahlrichs, J. Chem. Phys., 1996, 104, 9047; DOI: https://doi.org/10.1063/1.471637.
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Based on the materials of the VI North Caucasus Symposium on Organic Chemistry NCOCS-2022 (April 18–22, 2022, Stavropol, Russia).
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2595–2604, December, 2022.
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Nikolaeva, E.V., Aristov, I.V., Chachkov, D.V. et al. A quantum chemical study of the mechanism of thermal decomposition of N′-methoxy-N-methyldiazene N-oxide. Russ Chem Bull 71, 2595–2604 (2022). https://doi.org/10.1007/s11172-022-3688-7
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DOI: https://doi.org/10.1007/s11172-022-3688-7